Nu-substituted alkenyloxyacetamides



Patented Apr. 18, 1950 UNITED'STATES PATENT OFFICE N-SUBSTITUTEDALKENYLOXYACET- ALHDES Lowell B. Kilgore, Washington, D. C.

No Drawing.

18 Claims. 1

ROCHzCONHR' wherein R. is alkenyl and R represents a hydrocarbonradical.

A further object of this invention is to provide processes for thepreparation of these compounds.

Still a further object is the preparation of new compositions of matterwhich are useful as insectifuges and insecticides.

These and other objects will be apparent from the following moredetailed description:

The new compounds of this invention may be prepared by reacting aprimary amine with an alkenyloxyacetic acid, an alkenyloxyacetyl halideor an ester of an alkenyloxyacetic acid with a volatile alcohol. Thereaction mixtures are heated for varying periods of time depending onthe reactivities of the individual components. A slight excess of one Ofthe components is generally employed. It has been found thatsatisfactory yields are obtained without the use of solvents in thereaction mixture. However, a suitable inert diluent such as benzene ortoluene may be used. Where an acid chloride is employed the HCl formedmay be removed either by heat or by the incorporation of small amountsof a suitable organic base such as pyridine, :plperi- I dine and thelike. Where an ester is used, the volatile alcohol formed may bedistilled off. When the free acid is used the water of reaction may bedriven off by heat or removed by a dehydrating agent such as phosphoroustrichloride.

The more detailed practice of the invention is illustrated by thefollowing examples which, however, do not limit the scope oftheinvention in any way.

EXAMPLE 1 N-octyl allozcyacetamide gether for four hours.

Application August 19, 1947, Serial No. 769,515

sure. Sixteen grams of N-octyl alloxyacetamide, a water white liquidboiling at 132-135 C. at 3 mm. pressure, were obtained.

EXAMPLE 2 N-benzyl alloazyacetamz'de Twelve grams of alloxyacetic acidand ten grams of benzylamine were refluxed in an oil bath for fourhours. The water of reaction was distilled off under reduced pressureand the residue factionated. Eight and one-half grams of N- benzylalloxyacetamlde boiling at l40-140.5 C. at 2 mm. pressure were obtained.

EXAMPLE 3 N-cycZohemJ/Z crotoxyacetamide EXAMPLE 4 v N-allylmethalloxyacetamide Thirty grams of methyl methalloxyacetate and twelvegrams of allyl amine were refluxed to- The reaction mixture was thendistilled slowly to action and to permit the reaction to go tocompletion. The residue was then fractionated under reduced pressure.Ten grams of N-allyl methalloxyacetamide, a water white liquid boilingat 94-96 C. at 2 mm. pressure were obtained.

EXAMPLE 5 N-methallyl methallomyacetamide Seventy-two grams of methylmethalloxya acetate and forty grams of methallylamine were refluxedtogether for a total of twenty hours. Thereaction mixture was thendistilled to remove the 1 alcohol of reaction and the residuefractionated series of N -substituted a-etherified acetamides by 4remove the alcohol of re- C. at a pressure of 2.5 mm.

means of the afore-described methods as follows:

The new N-substituted a-etherified acetamides of my invention possessvaluable insect combatting properties. They may be employed either asinsecticides or insectifuges. However, they are particularly effectiveas insect repellents. "The value of these new compounds for this latterpurpose is enhanced by their desirable physical properties since theyare for the most part nonviscous liquids whose color and odor are suchas to make them unobjectionable for human use.

Table I demonstrates the efiicacy of representative members of this newseries of organic compounds against the common house fly, Muscadomestica. The test procedure used was the Sandwich bait methodsubstantially as described in Soap, June 1939, page 103 ff. A coatingofmolasses was applied to one side of a strip of blotting paper and driedto a hard glossy surface. The molasses was then covered with a strip ofa special, thin, porous paper which had previously been immersed in afive per cent solution in alcohol of the compound to be tested and thendried until the alcohol had evaporated. For purposes of comparison onestrip was treated only with solvent and dried. The strips prepared inthis fashion were mounted on a board and introduced into a large cagecontaining more than 2,000 hungry house flies. By making observations atfrequent intervals, the duration of repellency, that is the length oftime which elapsed before the flies began to feed on the molassesthrough the treated tissues, was determined.

TABLE I Duration of repel-- lency to house N-Octyl alloxyacetamide 8hrs. 35 minJI N-Octyl methalloxyacetamide 6 hrs. 10 min. N-Octylcrotoxyacetamide (ihrs. 10 minfif N-Cyclohexyl crotoxyacetamidm... 4hrs.

Tested in 5 per cent concentration. hjldait still untouched at end ofthis period. Flies had to be fed at t is'point.

1 Bait treated with this compound continuously exposed to flies until itwas attacked on the sixth day. Flies led at 24-hour intervals a minimumto keep them from dying of starvation.

1 Bait treated with this compound continuosuly exposed to flies until itwas attacked late the third day. Flies fed at 24-hour intervals aminimum to keep them from-dying of starvation.

5 Bait treated with this compound continuously exposed to flies until itwas attacked late the second day. Flies fed at 24-hour intervalsa'minimum to keep them from dying of starvation.

tained with with representative members of my new compounds:

TABLE 11 Duration Compound oi Repelleney M in. N-Isobutylcrotoxyacetaniide 8 N-Oycl'ohe'xyl methalloxyacetamide 319 Furthermore,the new compounds of my invention possess insecticidal properties. TableIH-illustrates the efficacy of representative members of this new seriesof N-substituted a-etherified acetamides against house flies. The Peet-Grady-bio a'ssay technique was employed in these tests. The solutionswere made up in a deodorized kerosene base.

These new compounds of my invention may be employed by direct topicalapplication, or they may be incorporated into liquid or solidcarriers.They are especially useful as the active ingredients of insect-repellentlotions, creams, ointments and the like: They may be dissolved inliquiddiluents such as alcohol, aqueous alcohol, isopropanol, dimethylphthalate and hydrocarbon oils such as kerosene, or emulsified in water,ifnecessary with the aid of a suitable dispersing agent. If desired,they may be admixed with finely divided carriers such as diatomaceousearth, talc, pyrophylite, bentonite, etc.

Furthermore, these compounds may be combined with insecticidal materialssuch as pyr-ethrum,-rotenone,derris, cub, DDT and the like.

Such a combination is particularly effective bethat the principles ofthis invention may be embodied in other forms but within the scope ofthe appended claims.

Ielaim: 1'- The N-substituted having the-general formula:

ROCHzCONHR' wherein R is alkenyl and R is hydrocarbon.

2. 'The 'N-substituted .alkenyloxyacetamides having the general formula;

ROCHzCONHAlkyl alkenylexyacetamides wherein R is alken-yl.

3. The N-substituted having the general formula:

ROCI-IzCONI-ICycloalkyl alkenyloxyacetamides wherein'R is alkenyl.

4. The having the general formula:

N-substituted alkenyloxyacetamides ROCH2C0NHAlkenyl wherein R isalkenyl.

5. N-octyl alloxyacetamide.

6. N-methallyl methalloxyacetamide.

'7. N-cyclohexyl methalloxyacetamide.

8. The process of preparing N-substituted alkenyloxyacetamides whichcomprises reacting a compound of the general formula:

ROCHzCOZ wherein R is alkenyl and Z is a radical selected from the groupconsistin of hydroxyl, halogen and CY, Y being the hydrocarbon radicalof an esterifying volatile alcohol, with a primary amine of the generalformula:

RNHz

wherein R is hydrocarbon.

9. An insect combative composition of matter comprising as essentialactive ingredient an N- substituted alkenyloxy-acetamide having thegeneral formula:

ROCHzCONI-IR' wherein R is alkenyl and R is hydrocarbon, and. a carriertherefor.

10. An insect combative composition of matter comprising as essentialactive ingredient an N-substituted alkenyloxyacetamide having thegeneral formula:

ROCHzCONHAlkyl ROCHzCONHAlkenyl wherein R is alkenyl, and a carriertherefor.

13. An insect combative composition of matter comprising as essentialactive ingredient N- octyl alloxyacetamide and a carrier therefor.

14. An insect combative composition of matter comprising as essentialactive ingredient N- methallyl methalloxyacetamide and a carriertherefor.

15. An insect combative composition of matter comprising as essentialactive ingredient N- cyclohexyl methalloxyacetamide and a carriertherefor.

16. An insect combative composition of matter comprising as essentialactive ingredient an N-substituted alkenyloxyacetamide having thegeneral formula:

ROCHZCONHR' wherein R is alkenyl and R is hydrocarbon, dissolved in analiphatic alcohol.

1'7. An insect combative composition of matter comprising as essentialactive ingredient an N-substituted alkenyloxyacetamide having thegeneral formula:

ROCHzCONHR' wherein R is alkenyl and R is hydrocarbon, dissolved in ahydrocarbon solvent.

18. An insect combative composition of matter comprising as essentialactive ingredient an N-substituted alkenyloxyacetamide having thegeneral formula:

ROCHzCONHR' wherein R is alkenyl and R is hydrocarbon, dissolved inaqueous alcohol.

LOWELL B. KILGORE.

REFERENCES CITED The following references are of record in the "file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,169,578 Bruson et a] Aug. 15;1939 2,347,494 Meigs Apr. 25, 1944 2,382,433 McNally et al Aug. 14, 1945Kilgore Sept. 2, 1947

9. AN INSECT COMBATIVE COMPOSITION OF MATTER COMPRISING AS ESSENTIALACTIVE INGREDIENT AN NSUBSTITUTED ALKENYLOXY-ACETAMIDE HAVING THEGENERAL FORMULA: